(1RS,4RS,5RS,6SR)-6-endo-(benzyloxy)-5-exo-{[(t-butyl)dimethylsilyl]oxy}-7-oxabicyclo[2.2.1]heptan-2-one | 139391-31-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1RS,4RS,5RS,6SR)-6-endo-(benzyloxy)-5-exo-{[(t-butyl)dimethylsilyl]oxy}-7-oxabicyclo[2.2.1]heptan-2-one
• 英文别名: (1R,4R,5R,6R)-5-[tert-butyl(dimethyl)silyl]oxy-6-phenylmethoxy-7-oxabicyclo[2.2.1]heptan-2-one
• CAS: 139391-31-4；139491-27-3
• 化学式: C₁₉H₂₈O₄Si
• 分子量: 348.514
• InChiKey: ZPGHOZLWSJBUPI-XMTFNYHQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1RS,4RS,5RS,6SR)-6-endo-(benzyloxy)-5-exo-{[(t-butyl)dimethylsilyl]oxy}-7-oxabicyclo[2.2.1]heptan-2-one 在 四氯化钛 、 双(三甲基硅烷基)氨基钾 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成
  参考文献：
  名称：

  以呋喃为原料的环丙醇全合成

  摘要：

  从呋喃的Diels-Alder加合物到乙酸1-氰基乙烯基酯以高度立体选择性的方式制备了（±）-环果糖醇。

  DOI：

  10.1016/s0040-4039(00)79144-1
• 作为产物：
  描述：

  (+/-)-7-oxabicyclo<2.2.1>hept-5-en-2-one 在 咪唑 、 氟磺酸 、 间氯过氧苯甲酸 作用下， 生成 (1RS,4RS,5RS,6SR)-6-endo-(benzyloxy)-5-exo-{[(t-butyl)dimethylsilyl]oxy}-7-oxabicyclo[2.2.1]heptan-2-one
  参考文献：
  名称：

  Total stereoselective syntheses of β-C-manno-pyranosides and of β-C(1→3)-linked disaccharides

  摘要：

  (-)-7-氧杂双环[2.2.1]庚-5-烯-2-酮已被转化为 (-)-6-外-[(叔丁基)二甲基硅氧基氧]-7-内-苯基氧-8-氧杂双环[3.2.1]辛-3-烯-2-酮以及甲基 3,5-二-O-乙酰基-2,6-脱水-4-O-苯甲酰基-D-甘油-D-半乳糖庚酸酯，它们与 Me₂AlSPh 缩合形成一个单一的 aldol，进而转化为 β-D-甘露糖基epar-CH(OAc)(1→3)-α-L-古糖基epar-CH(SEt)(2) 衍生物。(C) 1999 Elsevier Science Ltd. 保留所有权利。

  DOI：

  10.1016/s0040-4039(99)00432-3

文献信息

• Synthesis of 4-Hydroxy-2,6-bis(hydroxymethyl)tetrahydropyran-2-carbaldehyde Derivatives
  作者：Debra Turner、Pierre Vogel

  DOI：10.1055/s-1998-1629

  日期：1998.3

  Cycloaddition of 1,3-dibromo-2-oxyallyl cation to 2-(benzyloxymethyl)furan provided a 8-oxabicyclo[3.2.1]hept-6-en-3-one derivative that was transformed into (2RS,3SR,4SR,5SR,6SR)-3,4-dibromo-2-benzyloxymethyl-2,6-bis(hydroxymethyl)-4-(methoxymethyloxy)tetrahydropyran. Selective protection and oxidation produced a protected 3,5-dibromo-4-hydroxy-2,6-bis(hydroxymethyl)tetrahydropyran-2-carbaldehyde that could be used to carry out cross-aldolisations, opening an approach to the synthesis of C-disaccharide analogues mimicking sialic acid glycosides.

  1,3-二溴-2-氧烯丙基阳离子与2-(苄氧基甲基)呋喃的环加成反应生成了一种8-氧双环[3.2.1]庚-6-烯-3-酮衍生物，该衍生物经过转化得到了(2RS,3SR,4SR,5SR,6SR)-3,4-二溴-2-苄氧基甲基-2,6-双(羟甲基)-4-(甲氧甲基氧)四氢呋喃。选择性保护和氧化反应生成了一个保护的3,5-二溴-4-羟基-2,6-双(羟甲基)四氢呋喃-2-甲醛，可用于进行交叉醛醇缩合反应，从而为合成模仿唾液酸糖苷的C-二糖类类似物开辟了一条新途径。
• Total stereoselective syntheses of β-C-manno-pyranosides and of β-C(1→3)-linked disaccharides
  作者：Patrick Gerber、Pierre Vogel

  DOI：10.1016/s0040-4039(99)00432-3

  日期：1999.4

  (-)-7-Oxabicyclo[2.2.1]hept-5-en-2-one has been converted to (-)-6-exo-[(tert-butyl)dimethylsilyloxy]-7-endo-benzyloxy-8-oxabicyclo[3.2.1]oct-3-en-2-one and methyl 3,5-di-O-acetyl-2,6-anhydro-4-O-benzoyl-D- glycero-D-galacto-heptouronate that were condensed with Me2AlSPh into a single aldol which was transformed into a beta-D-ManAp-CH(OAc)(1-->3)-alpha-L-GulAp-CH(SEt)(2) derivative. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.

  (-)-7-氧杂双环[2.2.1]庚-5-烯-2-酮已被转化为 (-)-6-外-[(叔丁基)二甲基硅氧基氧]-7-内-苯基氧-8-氧杂双环[3.2.1]辛-3-烯-2-酮以及甲基 3,5-二-O-乙酰基-2,6-脱水-4-O-苯甲酰基-D-甘油-D-半乳糖庚酸酯，它们与 Me₂AlSPh 缩合形成一个单一的 aldol，进而转化为 β-D-甘露糖基epar-CH(OAc)(1→3)-α-L-古糖基epar-CH(SEt)(2) 衍生物。(C) 1999 Elsevier Science Ltd. 保留所有权利。
• Total, asymmetric synthesis of hexoses and azasugars branched at C(5).
  作者：Jürgen Wagner、Pierre Vogel

  DOI：10.1016/s0040-4020(01)91030-0

  日期：1991.11

  The Diels-Alder adduct (-)-5 (a "naked sugar") of furan to 1-cyanovinyl (1R')-camphanate was converted into (+)-(1R,5S,6S,7S)-6-exo,7-exo-(isopropylidenedioxy)-2,8-dioxabicylo[3.2.1]octan-3-one and into (+)-(1R,5S,6S,7S)-7-endo-(benzyloxy)-6-exo-[(t-butyl)dimethylsilyl]oxy}-2,8-dioxabicyclo[3.2.1]-octan-3-one ((+)-17). Double methylation at C(4) gave the corresponding 5-deoxy-5-C-dimethyl furanurono-6,1-lactones (+)-42 and (+)-19, respectively. Stereoselective and successive methylation and benzyloxymethylation of (+)-(1R,5S,6S,7S)-6-exo,-7-exo-(isopropylidenedioxy)2,8-dioxabicyclo[3.2.1]octan-3-one gave (+)-(1R,4R,5S,6S,7S)4-exo-[(benzyloxy)methyl]-6-exo,7-exo-(isopropylidenedioxy)-4-endo-methyl-2,8-dioxabicyclo[3.2.1]octan-3-one ((+)-9). Highly stereoselective oxydative decarboxylation of lactones (+)-9 and (+)-19 led to 5-C-methyl-alpha-beta-D-talo-hexose ((-)-1) and to 6-deoxy-5-C-methyl-alpha-beta-L-arabino-hexose ((-)-2), respectively. Transformation of lactones (+)-9 and (+)-42 into the corresponding acyl azides and their Curtius rearrangements led to (5-ammonio-1,5-N-anhydro-5-deoxy-5-C-methyl-alpha-beta-D-talo-hexitol)-1-sulfonate ((+)-3) and to (5-ammonio-1,5-N-anhydro-5,6-dideoxy-5-C-methyl-alpha-beta-L-ribo-hexitol)1-sulfonate ((+)-4), respectively.
• Evidence for Stereoelectronic Control in the OsO4 Bis-hydroxylation of trans-Cyclohex-2-ene-1,4-diols. Synthesis of Differentially Protected myo-Inositol Derivatives
  作者：Odon Arjona、Alfonso de Dios、Joaquin Plumet、Beatriz Saez

  DOI：10.1021/jo00120a046

  日期：1995.7
• Stereoselective Synthesis of 8-Oxabicyclo[3.2.1]octane-2,3,4,6,7-pentols and Total Asymmetric Synthesis of 2,6-Anhydrohepturonic Acid Derivatives and ofβ-C-manno-Pyranosides Suitable for the Construction of (1→3)-C,C-Linked Trisaccharides
  作者：Patrick Gerber、Pierre Vogel

  DOI：10.1002/1522-2675(20010613)84:6<1363::aid-hlca1363>3.0.co;2-m

  日期：2001.6.13

  (tert-butyl)dimethylsilyl]oxy}-7-oxa-bicy clo[2.2.1]heptan-2-one ((+)-5) and its enantiomer (-)-5, obtained readily from the Diets-Alder addition of furan to 1-cyanovinyl acetate. can be converted with high stereoselectivity into 8-oxabicyclo[3.2.1]octane-2,3.4.6,7-pentol derivatives (see 23- 28 in Scheme 2). A precursor of them, (1R,2S,4R,5S,6S,7R,8R)-7-endo-(benzyloxy)-8-exo-hydroxy-3,9-dioxatricycl

  对映体纯 (+)-(1S4S,5S 6S)-6-endo-(benzyloxy)-5-exo-[(tert-butyl)dimethylsilyl]oxy}-7-oxa-bicy clo[2.2.1]heptan- 2-one ((+)-5) 及其对映异构体 (-)-5，很容易通过 Diets-Alder 将呋喃添加到 1-氰基乙酸乙烯酯中获得。可以以高立体选择性转化为 8-oxabicyclo[3.2.1]octane-2,3.4.6,7-pentol 衍生物（参见方案 2 中的 23-28）。它们的前体，(1R,2S,4R,5S,6S,7R,8R)-7-endo-(benzyloxy)-8-exo-hydroxy-3,9-dioxatricycl o[4.2.1.0(2.4)]non -.5-endo-yl benzoate ((-)-19), 转化为 (1R,2R,5S, 6S,7R